EP2880067B2 - Pipes - Google Patents
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- Publication number
- EP2880067B2 EP2880067B2 EP13742473.5A EP13742473A EP2880067B2 EP 2880067 B2 EP2880067 B2 EP 2880067B2 EP 13742473 A EP13742473 A EP 13742473A EP 2880067 B2 EP2880067 B2 EP 2880067B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- pipe
- range
- pipe according
- parts
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 229920001577 copolymer Polymers 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000002516 radical scavenger Substances 0.000 claims description 8
- 239000006078 metal deactivator Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- -1 polyethylene Polymers 0.000 description 48
- 239000004698 Polyethylene Substances 0.000 description 27
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 25
- 229920000573 polyethylene Polymers 0.000 description 23
- 239000000463 material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000004711 α-olefin Substances 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000035882 stress Effects 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000001475 halogen functional group Chemical group 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- 150000008040 ionic compounds Chemical class 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000010936 titanium Chemical group 0.000 description 5
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000002902 bimodal effect Effects 0.000 description 4
- 150000001642 boronic acid derivatives Chemical class 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 230000002706 hydrostatic effect Effects 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002879 Lewis base Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000007527 lewis bases Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000002897 diene group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 description 2
- 150000004678 hydrides Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003534 oscillatory effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002989 phenols Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- ZCBSOTLLNBJIEK-UHFFFAOYSA-N silane titanium Chemical compound [SiH4].[Ti] ZCBSOTLLNBJIEK-UHFFFAOYSA-N 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Chemical group 0.000 description 2
- YDFSEGHMSGCLHG-UHFFFAOYSA-N (2-hydroxy-3,4,5-triphenylphenoxy)boronic acid Chemical compound C=1C=CC=CC=1C=1C(C=2C=CC=CC=2)=C(O)C(OB(O)O)=CC=1C1=CC=CC=C1 YDFSEGHMSGCLHG-UHFFFAOYSA-N 0.000 description 1
- KGLYHHCCIBZMLN-UHFFFAOYSA-N 1-methyl-4-[4-(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C=CC=CC1=CC=C(C)C=C1 KGLYHHCCIBZMLN-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical class CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- MLJRLEGXZUNRLY-UHFFFAOYSA-N 2,4-ditert-butylphenol;phosphorous acid Chemical compound OP(O)O.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 MLJRLEGXZUNRLY-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OMCYEZUIYGPHDJ-UHFFFAOYSA-N 2-hydroxy-N-[(2-hydroxyphenyl)methylideneamino]benzamide Chemical compound OC1=CC=CC=C1C=NNC(=O)C1=CC=CC=C1O OMCYEZUIYGPHDJ-UHFFFAOYSA-N 0.000 description 1
- UORSDGBOJHYJLV-UHFFFAOYSA-N 2-hydroxy-n'-(2-hydroxybenzoyl)benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)C1=CC=CC=C1O UORSDGBOJHYJLV-UHFFFAOYSA-N 0.000 description 1
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- AJNFVEGCEDTQKG-UHFFFAOYSA-N [2-hydroxy-3,4,5-tris(2,3,4,5,6-pentafluorophenyl)phenoxy]boronic acid Chemical compound FC=1C(F)=C(F)C(F)=C(F)C=1C=1C(C=2C(=C(F)C(F)=C(F)C=2F)F)=C(O)C(OB(O)O)=CC=1C1=C(F)C(F)=C(F)C(F)=C1F AJNFVEGCEDTQKG-UHFFFAOYSA-N 0.000 description 1
- BVYOMXWAJZACIU-UHFFFAOYSA-N [2-hydroxy-3,4,5-tris(4-methylphenyl)phenoxy]boronic acid Chemical compound C1=CC(C)=CC=C1C1=CC(OB(O)O)=C(O)C(C=2C=CC(C)=CC=2)=C1C1=CC=C(C)C=C1 BVYOMXWAJZACIU-UHFFFAOYSA-N 0.000 description 1
- HAAZCIDUOSCCQU-UHFFFAOYSA-N [4-hydroxy-2,3,5-tris(2,3,4,5,6-pentafluorophenyl)phenoxy]boronic acid Chemical compound FC=1C(F)=C(F)C(F)=C(F)C=1C=1C(OB(O)O)=CC(C=2C(=C(F)C(F)=C(F)C=2F)F)=C(O)C=1C1=C(F)C(F)=C(F)C(F)=C1F HAAZCIDUOSCCQU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
- YSRFHVJGXPIDGR-UHFFFAOYSA-N dimethylsilane titanium Chemical compound [Ti].C[SiH2]C YSRFHVJGXPIDGR-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 description 1
- KUFYUMSBZMUWAN-UHFFFAOYSA-N n-methyl-n-tetradecyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCC KUFYUMSBZMUWAN-UHFFFAOYSA-N 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/02—Protection of pipes or objects of similar shape against external or internal damage or wear against cracking or buckling
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
- F16L9/127—Rigid pipes of plastics with or without reinforcement the walls consisting of a single layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
Definitions
- High density polyethylene in particular is known to have a good mechanical strength at elevated temperatures and has been used in packaging applications where a good high temperature performance is required.
- HDPE High density polyethylene
- the long term hydrostatic strength characteristics of non crosslinked HDPE materials at higher temperatures are often unsuitable for applications such as hot water pipes.
- EP 1425344 describes multimodal polyethylenes having a density in the range about 925 to about 950 kg/m 3 and melt index in the range about 0.1 to about 5 g/10 min for use in durable applications such as pipes and exhibit an excellent stress performance at higher temperatures.
- EP 1448702 describes pipes for hot fluids comprising multimodal polyethylenes with density in the range 921 to 950 kg/m 3 .
- the pipes of the present invention exhibit improved chlorine resistance, improved resistance to slow crack growth as well as improved pipe creep resistance.
- Chlorine resistance is defined by means of the extrapolated time to failure according to ASTM F2023 and ASTM F2769-10. Resistance to slow crack growth is defined by a time to failure according to ISO 13479 and pipe creep resistance according to ISO 1167.
- the copolymers used to the pipe also exhibit good flexibility characterised, for instance, by a tensile modulus at 23°C and a deformation rate of 1 mm/min according to ISO 527-2 lower than 900 MPa, preferably lower than 700 MPa.
- the copolymers according to the present invention have a unimodal molecular weight distribution.
- unimodal molecular weight distribution is meant a copolymer that does not contain fractions of substantially different molecular weights.
- substantially different molecular weights it must be understood that, in the case of production in several reactors in series, the difference in the weight average molecular weight of the polymer, as determined by conventional gel permeation chromatography (GPC), produced in each reactor is not greater than 10%.
- the most preferred support material for use with the supported catalysts according to the method of the present invention is silica.
- Suitable supports are silicas having a median diameter (d50) from 20 to 70 ⁇ m, preferably from 30 to 60 ⁇ m.
- Particularly suitable supports of this type are Grace Davidson D948 or Sylopol 2408 silicas as well as PQ Corporation ES70 or ES757 silicas.
- ethylene and 1-hexene Alternatively a combination of one or more monomers may be used for example ethylene and 1-hexene.
- novel copolymers of the present invention may be suitably prepared by the copolymerisation of ethylene with alpha-olefins.
- a first antioxidant comprising phosphites or phosphonites such as tris (2,4-ditert-butylphenol) phosphite (IrgafosTM 168) is advantageously used in the formulation.
- the composition preferably contains from 0.01 to 0.3 parts of the first antioxidant per 100 parts of polymer, more preferably from 0.02 to 0.2 parts, contents from 0.05 to 0.15 parts being particularly preferred.
- copolymer of example 1 was extruded in various standard pipe dimensions, and the properties of the pipes were evaluated according to the relevant standard methods.
Description
- The present invention relates to pipes and in particular to large diameter pipes suitable for use in industrial applications such as desalination, offshore, industrial/waste water conveying systems, district heating and geothermal applications. The pipes comprise copolymers of ethylene and α-olefins and in particular to copolymers prepared by use of metallocene catalyst systems.
- In the past polyethylene materials were cross-linked in order to achieve the desired high temperature requirements in particular long term strength for use in hot water pipe applications.
- Monomodal polyethylenes such as medium density (MDPE) having densities in the range 930 - 942 kg/m3 and high density polyethylenes (HDPE) having density in the range 945 - 965 kg/m3 have been used for applications in the temperature range of about 0°C to about 50°C.
- High density polyethylene (HDPE) in particular is known to have a good mechanical strength at elevated temperatures and has been used in packaging applications where a good high temperature performance is required. However the long term hydrostatic strength characteristics of non crosslinked HDPE materials at higher temperatures are often unsuitable for applications such as hot water pipes.
- These Polyethylenes of Raised Temperature Resistance (PE-RT) materials have been used successfully for many years in domestic and industrial hot water piping systems and also as part of underfloor heating and radiator connections. More recently the easy processing and outstanding material properties have made such materials useful in larger diameter industrial applications where standard polyethylene materials cannot be used due to high temperature limitations.
- For such applications the required technical attributes of the polymers are excellent creep resistance at high temperature, good heat stability in chlorinated water environments, good processability and high flexibility.
- More recently polymers having a multimodal molecular weight distribution have been used successfully for use in hot water pipe applications. Polyethylene compositions with a multimodal molecular weight distribution (MWD) for example a bimodal MWD can offer advantages compared with prior art unimodal polyethylenes. For example bimodal polyethylenes may combine the favorable mechanical properties afforded by high molecular weight polyethylene with the good processability of low molecular weight polyethylene.
- Peroxide cross-linking of polymers has also been found to show some improvement in the creep resistance of the polymers at high temperature.
- Prior art multimodal polyethylenes for use in pipe applications are described in
WO 97/29152 WO 00/01765 WO 00/18814 WO 01/92480 WO 01/25328 EP 1425344 describes multimodal polyethylenes having a density in the range about 925 to about 950 kg/m3 and melt index in the range about 0.1 to about 5 g/10 min for use in durable applications such as pipes and exhibit an excellent stress performance at higher temperatures.EP 1448702 describes pipes for hot fluids comprising multimodal polyethylenes with density in the range 921 to 950 kg/m3. -
WO 05/056657 - More recently
WO 08/064810 - Other references teaching the use of bimodal or multimodal polyethylenes for use in pipe applications include
US 2010/0092709 ,EP 1927626 ,EP 1764385 ,EP 1146079 andEP 1425344 . None of these teach advantages such as resistance to chlorine or pressure resistance at very high temperatures (110°C/2.6 MPa). - Our earlier application
WO 06/120418 - Our earlier application
WO 10/000557 - We have now surprisingly found that pipes comprising certain metallocene derived copolymers of ethylene and α-olefins may be suitable for use in industrial applications, in particular for use in large diameter pipes. The pipes according to this aspect of the present invention exhibit an improved resistance to chlorine as well as improved resistance to slow crack growth.
- Thus according to the present invention there is provided a pipe having an outer diameter of from 90 to 630 mm and a minimum wall thickness higher than 3.6mm, said pipe having
- (a) an extrapolated time-to-failure according to ASTM F2023 and ASTM F2769-10 (performed on 16 mm SDR 7.4 pipe) of at least 50 years (for classification code CL5),
- (b) a time to failure according to ISO 1167 (performed on 32 mm SDR 11 pipe) of at least 10000 hours (at 110°C under hoop stress of 2.6 MPa), and
- (c) a resistance to slow crack growth according to ISO 13479 (80°C, 9.2 bar, performed on 110 mm SDR 11 notched pipe) of at least 5000 hrs,
said pipe comprising a copolymer of ethylene and an α-olefin, said copolymer characterized in having a unimodal molecular weight distribution and - (a) a density (D) in the range 933 - 948 kg/m3
- (b) a melt index (MI2) in the range 0.15 - 2.0 g/10 min, and
- (c) a melt elastic modulus G' (G"= 500 Pa) in the range 40 to 150 Pa.
- Pipes made from such copolymers have been found to exhibit the balance of favorable mechanical properties afforded by high molecular weight polyethylene with the good processability of low molecular weight polyethylene previously seen with multimodal polymers. In addition, excellent long-term hydrostatic strength is obtained without any crosslinking of the polyethylene material.
- The pipes of the present invention exhibit improved chlorine resistance, improved resistance to slow crack growth as well as improved pipe creep resistance.
- Chlorine resistance is defined by means of the extrapolated time to failure according to ASTM F2023 and ASTM F2769-10. Resistance to slow crack growth is defined by a time to failure according to ISO 13479 and pipe creep resistance according to ISO 1167.
- While the present invention is directed to pipes having an outer diameter of at least 90 mm, the defined parameters of chlorine resistance, resistance to slow crack growth and pipe creep resistance are determined in accordance with the standard procedures performed on pipes having defined diameters and Standard Dimension Ratios (SDR).
- For classification code CL5 according to ASTM F2023 and ASTM F2769-10, the pipe preferably has a time-to-failure of at least 60 years. For classification code CL3 according to ASTM F2023 and ASTM F2769-10, the pipe preferably has an extrapolated time-to-failure of at least 100 years, more preferably of at least 125 years.
- In a preferred embodiment of the invention, the pipe made from such copolymers has superior resistance at high temperature in hydrostatic pressure testing which enable to classify it as PE-RT type II according to ISO 22391:2009. In addition, the long term hydrostatic strength of the said pipe enables it to be attributed a MRS rating of at least 8 MPa according to standard ISO 9080.
- In another preferred embodiment, the pipe of the present invention preferably exhibits very good resistance to rapid propagation of cracks (RCP), reflected by a halting of crack propagation at an internal pressure equal to at least 10 bars, as measured at 0°C on a pipe of SDR 11 with diameter 110 mm and thickness 10 mm according to method S4 described in ISO 13477:2008.
- The pipe of the present invention has an outer diameter of from 90 to 630 mm, more preferably from 110 to 315 mm. The minimum wall thickness of the said pipe is higher than 3.6 mm, preferably between 6.3 and 28.6 mm, and more preferably between 10 and 20 mm.
- The copolymers used to the pipe also exhibit good flexibility characterised, for instance, by a tensile modulus at 23°C and a deformation rate of 1 mm/min according to ISO 527-2 lower than 900 MPa, preferably lower than 700 MPa.
- Preferred alpha-olefins are those having C4 - C12 carbon atoms. Most preferred alpha-olefins are 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.
- The preferred alpha-olefin is 1-hexene.
- The copolymers according to the present invention preferably have a density in the range 933 - 940 kg/cm3 and more preferably in the range 935 - 940 kg/cm3.
- The copolymers according to the present invention preferably have a melt index (MI2 measured under a load of 2.16 kg) in the range 0.8 to 1.5 and more preferably in the range 1.0 - 1.3 g/10 min.
- The copolymers according to the present invention also exhibit a melt index (MI5 measured under a load of 5 kg) in the range 0.5 to 6.0, preferably in the range 1.0 to 5.0 and most preferably in the range 2.0 to 4.0.
- The copolymers according to the present invention preferably have a melt elastic modulus G' (G" = 500 Pa) in the range 40 - 100 and most preferably in the range 40 to 70 Pa.
- The copolymers according to the present invention preferably have a Composition Distribution Branch Index (CDBI) in the range 55 - 75% and preferably in the range 58 - 72%.
- The copolymers according to the present invention may exhibit a ratio of complex dynamic shear viscosities η*(0.1)/ η*(100) in the range 1.5 to 5.5 preferably in the range 2.0 - 5.0 and most preferably in the range 2.5 - 4.5.
- The copolymers according to the present invention have a unimodal molecular weight distribution. By unimodal molecular weight distribution is meant a copolymer that does not contain fractions of substantially different molecular weights. By substantially different molecular weights, it must be understood that, in the case of production in several reactors in series, the difference in the weight average molecular weight of the polymer, as determined by conventional gel permeation chromatography (GPC), produced in each reactor is not greater than 10%.
- The copolymers of the present invention typically exhibit a molecular weight distribution (Mw/Mn) in the range 3.5 to 10 and preferably in the range 3.5 to 8.0.
- The copolymers of the present invention may suitably be prepared by use of a single site catalyst system for example a metallocene catalyst system comprising, preferably a monocylcopentadienyl metallocene complex having a 'constrained geometry' configuration together with a suitable cocatalyst.
- Examples of monocyclopentadienyl or substituted monocyclopentadienyl complexes suitable for use in the present invention are described in
EP 416815 EP 418044 EP 420436 EP 551277 - Suitable complexes may be represented by the general formula:
CpMXn
wherein Cp is a single cyclopentadienyl or substituted cyclopentadienyl group optionally covalently bonded to M through a substituent, M is a Group VIA metal bound in a η5 bonding mode to the cyclopentadienyl or substituted cyclopentadienyl group, X each occurrence is hydride or a moiety selected from the group consisting of halo, alkyl, aryl, aryloxy, alkoxy, alkoxyalkyl, amidoalkyl, siloxyalkyl etc. having up to 20 non-hydrogen atoms and neutral Lewis base ligands having up to 20 non-hydrogen atoms or optionally one X together with Cp forms a metallocycle with M and n is dependent upon the valency of the metal. -
- R' each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said R' having up to 20 nonhydrogen atoms, and optionally, two R' groups (where R' is not hydrogen, halo or cyano) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a fused ring structure;
- X is hydride or a moiety selected from the group consisting of halo, alkyl, aryl, aryloxy, alkoxy, alkoxyalkyl, amidoalkyl, siloxyalkyl etc. having up to 20 non-hydrogen atoms and neutral Lewis base ligands having up to 20 non-hydrogen atoms,
- Y is -O-, -S-, -NR*-, -PR*-,
- M is hafnium, titanium or zirconium,
- Z* is SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2, or
- GeR*2, wherein:
- R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said
- R* having up to 10 non-hydrogen atoms, and optionally, two R* groups from Z* (when R* is not hydrogen), or an R* group from Z* and an R* group from Y form a ring system.,
- and n is 1 or 2 depending on the valence of M.
- Examples of suitable monocyclopentadienyl complexes are (tert-butylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silanetitanium dichloride and (2-methoxyphenylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silanetitanium dichloride.
-
- R' each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said R' having up to 20 nonhydrogen atoms, and optionally, two R' groups (where R' is not hydrogen, halo or cyano) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a fused ring structure;
- X is a neutral η4 bonded diene group having up to 30 non-hydrogen atoms, which forms a π-complex with M;
- Y is -O-, -S-, -NR*-, -PR*-,
- M is titanium or zirconium in the + 2 formal oxidation state;
- Z* is SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2, or
- GeR*2, wherein:
- R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said
- R* having up to 10 non-hydrogen atoms, and optionally, two R* groups from Z* (when R* is not hydrogen), or an R* group from Z* and an R* group from Y form a ring system.
- Examples of suitable X groups include s-trans-η4-1,4-diphenyl-1,3-butadiene, s-trans-η4-3-methyl-1,3-pentadiene; s-trans-η4-2,4-hexadiene; s-trans-η4-1,3-pentadiene; s-trans-η4-1,4-ditolyl-1,3-butadiene; s-trans-η4-1,4-bis(trimethylsilyl)-1,3)-butadiene; s-cis-η4-3-methyl-1,3-pentadiene; s-cis-η4-1,4-dibenzyl-1,3-butadiene; s-cis-η4-1,3-pentadiene; s-cis-η4-1,4-bis(trimethylsilyl)-1,3-butadiene, said s-cis diene group forming a π-complex as defined herein with the metal.
- Most preferably R' is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, or phenyl or 2 R' groups (except hydrogen) are linked together, the entire C5R'4 group thereby being, for example, an indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl group.
- Highly preferred Y groups are nitrogen or phosphorus containing groups containing a group corresponding to the formula -N(R//)- or -P(R//)- wherein R// is C1-10 hydrocarbyl.
- Most preferred complexes are amidosilane - or amidoalkanediyl complexes.
- Most preferred complexes are those wherein M is titanium.
- Specific complexes are those disclosed in
WO 95/00526 - A particularly preferred complex is (t-butylamido) (tetramethyl-η5-cyclopentadienyl) dimethyl silanetitanium - η4-1.3-pentadiene.
- Suitable cocatalysts for use in the preparation of the novel copolymers of the present invention are those typically used with the aforementioned metallocene complexes.
- These include aluminoxanes such as methyl aluminoxane (MAO), boranes such as tris(pentafluorophenyl) borane and borates.
- Aluminoxanes are well known in the art and preferably comprise oligomeric linear and/or cyclic alkyl aluminoxanes. Aluminoxanes may be prepared in a number of ways and preferably are prepare by contacting water and a trialkylaluminium compound, for example trimethylaluminium, in a suitable organic medium such as benzene or an aliphatic hydrocarbon.
- A preferred aluminoxane is methyl aluminoxane (MAO).
- Other suitable cocatalysts are organoboron compounds in particular triarylboron compounds. A particularly preferred triarylboron compound is tris(pentafluorophenyl) borane.
- Other compounds suitable as cocatalysts are compounds which comprise a cation and an anion. The cation is typically a Bronsted acid capable of donating a proton and the anion is typically a compatible non-coordinating bulky species capable of stabilizing the cation.
- Such cocatalysts may be represented by the formula:
(L*-H)+ d(Ad-)
wherein - L* is a neutral Lewis base
- (L*-H)+ d is a Bronsted acid
- Ad- is a non-coordinating compatible anion having a charge of d-, and
- d is an integer from 1 to 3.
- The cation of the ionic compound may be selected from the group consisting of acidic cations, carbonium cations, silylium cations, oxonium cations, organometallic cations and cationic oxidizing agents.
- Suitably preferred cations include trihydrocarbyl substituted ammonium cations eg. triethylammonium, tripropylammonium, tri(n-butyl)ammonium and similar. Also suitable are N.N-dialkylanilinium cations such as N,N-dimethylanilinium cations.
- The preferred ionic compounds used as cocatalysts are those wherein the cation of the ionic compound comprises a hydrocarbyl substituted ammonium salt and the anion comprises an aryl substituted borate..
- Typical borates suitable as ionic compounds include:
- triethylammonium tetraphenylborate
- triethylammonium tetraphenylborate,
- tripropylammonium tetraphenylborate,
- tri(n-butyl)ammonium tetraphenylborate,
- tri(t-butyl)ammonium tetraphenylborate,
- N,N-dimethylanilinium tetraphenylborate,
- N,N-diethylanilinium tetraphenylborate,
- trimethylammonium tetrakis(pentafluorophenyl) borate,
- triethylammonium tetrakis(pentafluorophenyl) borate,
- tripropylammonium tetrakis(pentafluorophenyl) borate,
- tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,
- N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,
- N,N-diethylanilinium tetrakis(pentafluorophenyl) borate.
- A preferred type of cocatalyst suitable for use with the metallocene complexes comprise ionic compounds comprising a cation and an anion wherein the anion has at least one substituent comprising a moiety having an active hydrogen.
- Suitable cocatalysts of this type are described in
WO 98/27119 - Examples of this type of anion include:
- triphenyl(hydroxyphenyl) borate
- tri (p-tolyl)(hydroxyphenyl) borate
- tris (pentafluorophenyl)(hydroxyphenyl) borate
- tris (pentafluorophenyl)(4-hydroxyphenyl) borate
- Examples of suitable cations for this type of cocatalyst include triethylammonium, triisopropylammonium, diethylmethylammonium, dibutylethylammonium and similar.
- Particularly suitable are those cations having longer alkyl chains such as dihexyldecylmethylammonium, dioctadecylmethylammonium, ditetradecylmethylammonium, bis(hydrogentated tallow alkyl) methylammonium and similar.
- Particular preferred cocatalysts of this type are alkylammonium tris(pentafluorophenyl) 4-(hydroxyphenyl) borates. A particularly preferred cocatalyst is bis(hydrogenated tallow alkyl) methyl ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate.
- With respect to this type of cocatalyst, a preferred compound is the reaction product of an alkylammonium tris(pentaflurophenyl)-4-(hydroxyphenyl) borate and an organometallic compound, for example triethylaluminium or an aluminoxane such as tetraisobutylaluminoxane.
- The catalysts used to prepare the novel copolymers of the present invention may suitably be supported.
- Suitable support materials include inorganic metal oxides or alternatively polymeric supports may be used for example polyethylene, polypropylene, clays, zeolites, etc.
- The most preferred support material for use with the supported catalysts according to the method of the present invention is silica. Suitable supports are silicas having a median diameter (d50) from 20 to 70 µm, preferably from 30 to 60 µm. Particularly suitable supports of this type are Grace Davidson D948 or Sylopol 2408 silicas as well as PQ Corporation ES70 or ES757 silicas.
- The support material may be subjected to a heat treatment and/or chemical treatment to reduce the water content or the hydroxyl content of the support material. Typically chemical dehydration agents are reactive metal hydrides, aluminium alkyls and halides. Prior to its use the support material may be subjected to treatment at 100°C to 1000°C and preferably at 200 to 850°C in an inert atmosphere under reduced pressure.
- The porous supports are preferably pretreated with an organometallic compound preferably an organoaluminium compound and most preferably a trialkylaluminium compound in a dilute solvent.
- The support material is pretreated with the organometallic compound at a temperature of -20°C to 150°C and preferably at 20°C to 100°C.
- Suitable catalysts for use in the preparation of the novel copolymers of the present invention are suitably described in
WO 04/020487 WO 05/019275 - Particularly suitable catalysts for use in the preparation of the copolymers of the present invention are metallocene complexes which have been treated with polymerisable monomers. Our earlier applications
WO 04/020487 WO 05/019275 - Polymerisable monomers suitable for use in this aspect of the present invention include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, styrene, butadiene, and polar monomers for example vinyl acetate, methyl methacrylate, etc. Preferred monomers are those having 2 to 10 carbon atoms in particular ethylene, propylene, 1-butene or 1-hexene.
- Alternatively a combination of one or more monomers may be used for example ethylene and 1-hexene.
- The preferred polymerisable monomer is 1-hexene.
- The polymerisable monomer is suitably used in liquid form or alternatively may be used in a suitable solvent. Suitable solvents include for example heptane.
- The polymerisable monomer may be added to the cocatalyst before addition of the metallocene complex or alternatively the complex may be pretreated with the polymerisable monomer.
- The copolymers of the present invention are preferably prepared in a single reactor.
- The novel copolymers of the present invention may suitably be prepared in processes performed in either the slurry or the gas phase.
- A slurry process typically uses an inert hydrocarbon diluent and temperatures from about 0°C up to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert copolymerizing medium. Suitable diluents include toluene or alkanes such as hexane, propane or isobutane. Preferred temperatures are from about 30°C up to about 200°C but preferably from about 60°C to 100°C. Loop reactors are widely used in slurry copolymerizing processes.
- The novel copolymers are most suitably prepared in a gas phase process.
- Gas phase processes for the copolymerizing of olefins, especially for the homopolymerisation and the copolymerization of ethylene and α-olefins for example 1-butene, 1-hexene, 4-methyl-1-pentene are well known in the art.
- Typical operating conditions for the gas phase are from 20°C to 100°C and most preferably from 40°C to 90°C with pressures from subatmospheric to 100 bar.
- Particularly preferred gas phase processes are those operating in a fluidized bed. Examples of such processes are described in
EP 89691 EP 699213 - The novel copolymers of the present invention may be suitably prepared by the copolymerisation of ethylene with alpha-olefins.
- The preferred alpha-olefins are 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. The most preferred alpha-olefin is 1-hexene.
- Thus according to another aspect of the present invention there is provided a method for the preparation of copolymers of ethylene and alpha-olefins, suitable for use in pipes having an outer diameter of at least 90 mm, said copolymers having
- (a) a density (D) in the range 933 - 948 kg/m3
- (b) a melt index (MI2) in the range 0.15 - 2.0 g/10 min, and
- (c) a melt elastic modulus G' (G"= 500 Pa) in the range 40 to 150 Pa,
- The novel copolymers of the present invention are most suitably used together with additive packages which operate synergistically for the environment of a pipe for use in for example chlorinated water supply. For example antioxidants and other additives may be chosen for performance with respect to the atmosphere external to the pipe and also for performance with respect to the chlorine exposure in the interior of the pipe.
- A first antioxidant comprising phosphites or phosphonites such as tris (2,4-ditert-butylphenol) phosphite (Irgafos™ 168) is advantageously used in the formulation. The composition preferably contains from 0.01 to 0.3 parts of the first antioxidant per 100 parts of polymer, more preferably from 0.02 to 0.2 parts, contents from 0.05 to 0.15 parts being particularly preferred.
- A second class of specific antioxidants that provides efficient protection to long term ageing particularly when exposed to water medium can also be advantageously used. For instance, low polarity hindered phenols bearing non-hydrolysable organic functions are suitable to guarantee a good dispersion of the antioxidant in the polymer matrix , but also excellent long term stability and low leaching of additive by-products in the aqueous medium. Other antioxidants with slow kinetic of hydrolysis like hydroxylamines, hindered amines light stabilizers (like derivatives of 2,2,6,6-tetramethyl piperidine) or thiosynergists organosulfides (like distearyl thiodipropionate) can also be used. Among the different antioxidants, specific hindered phenols like 3,3',3", 5, 5',5"-hexa-tert-butyl α, α', α"-(mesitylene-2,4,6-trityl) tri-p-cresol (Irganox™ 1330, Ethanox™ 1330) or 1,3,5-tris(3,5-di-tert-buty1-4-hydroxybenzy1)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Irganox™ 3114) are preferred. Irganox™ 1330 is particularly preferred. The composition preferably contains from 0.05 to 1 part of the second antioxidant per 100 parts of polymer, more preferably from 0.1 to 0.5 part, contents from 0.15 to 0.30 part being particularly preferred.
- A metal deactivator such as, for example N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine, N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene)oxallyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis (salicyloyl)oxallyl dihydrazide, N,-N'-bis(salicyloyl)thiopropionyl dihydrazide, is also advantageously used in the composition. N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine (Evernox™ MD 1024). The composition preferably contains from 0.01 to 0.3 parts of metal deactivator per 100 parts of polymer, more preferably from 0.02 to 0.2 parts, contents from 0.05 to 0.15 parts being particularly preferred.
- An acid scavenger may also be advantageously used in the formulation. Metal soaps, metal oxide or hydrotalcite are known to be suitable acid scavengers. When such an acid scavenger is used, metal soaps like zinc stearate or calcium stearate or metal oxides like zinc oxide are preferred. Zinc oxide is the most preferred acid scavenger. The composition preferably contains less than 0.25 parts of the acid scavenger per 100 parts of polymer, more preferably less than 0.15 parts per 100 parts polymer and most preferably less than 0.1 parts per 100 parts polymer.
- Optionally, a third antioxidant may be used in the additive package. This third antioxidant is generally a hindered phenol bearing hydrolysable organic function for example Irganox™ 1010, Irganox™ 1076, or Cyanox™ 1790. The composition preferably contains less than 0.3 part of the first antioxidant per 100 parts of polymer, more preferably less than 0.2 part, contents of less than 0.1 part being particularly preferred.
- In addition processing aids, UV stabilizers, pigments or colorants may also be used in the additive package.
- A typical additive package comprises 0.1 parts of the first antioxidant (Irgafos™ 168), 0.25 parts of the second antioxidant (Irganox™ 1330), 0.1 part of metal deactivator (Evernox™ MD 1024) and 0.05 parts of acid scavenger (zinc oxide) per 100 parts of the polymer composition.
- Thus according to another aspect of the present invention there is provided a pipe according to the present invention having an antioxidant system comprising (a) a single hindered phenol (b) at least one phosphite, (c) at least one metal deactivator and (d) an acid scavenger.
- The present invention will now be further illustrated by reference to the following examples.
- Under continuous agitation, 1491 L of isohexane and 397 kg of silica D948 (available from W.R. Grace), were added to a reactor. (The silica had been previously calcined under nitrogen to reach a level of hydroxyl groups of 1.53 mmol/g). 19.3 kg of an Octastat 2000 (available from Innospec) solution in pentane (2g/l) was then added and the mixture was stirred for 15 minutes. 571 kg of a 12% triethylaluminium (TEA) solution in isohexane was then slowly added over 1 hour and the mixture was stirred for 1 hour further at 30°C. The slurry was filtered and thoroughly washed with isohexane before being transferred to a dryer. 19 kg of an Octastat 2000 solution in pentane (2g/l) was added and the mixture was finally dried at 60°C under vacuum. 428 kg of silica/TEA were obtained. The aluminium content of the solid was found to be 1.3 mmol/g.
- To 216.9 kg of a 9.58% solution of [N(H)Me(C18-22H37-45)2] [B(C6F5)3(p-OHC6H4)] (Ionic Compound A) in toluene were added over 15 minutes 17.75 kg of 11.7 % TEA solution in isohexane. The mixture was further stirred for 15 minutes to yield a solution of catalyst component 1.
- To 53.0 kg of a 11.6 % solution of Complex A in heptane were added 47.8 kg of 1-hexene.
- 288 kg of the above prepared silica/TEA was introduced into a reactor. The above prepared solution of catalyst component 1 was fed to the reactor over 45 minutes and the mixture was then stirred for further 30 minutes. The contents of the reactor were then cooled to 15°C and the above prepared solution of Complex A and 1-hexene was fed over a period of 30 minutes, and then the mixture was further stirred for 1 hour. During the addition the internal temperature increased to a maximum of 23°C. 34 kg of an Octastat 2000 solution in pentane (2g/l) was then added and the mixture was dried at 45°C until the residual solvent content in the catalyst was <1%.
Analysis of the resulting dry powder showed the titanium content to be 44.0 µmol/g, the boron content to be 53.7 µmol/g and the aluminium content to be 1.02 mmol/g. - The copolymers according to the present invention were prepared by copolymerisation of ethylene with hexene in a gas phase fluidized bed reactor having a 5.5 m diameter and using the catalyst system prepared above.
- Process conditions were as follows:
Table 1 Temperature °C 85 Ethylene partial pressure bar 12 Hydrogen/ethylene ratio mol/mol 0.002 Hexene/ethylene ratio mol/mol 0.0035 Pentane partial pressure bar 3.3 Production rate ton/h 17 Space time yield kg/h/m3 56 - The polyethylene powder was compounded under nitrogen atmosphere on ZSK240 extruders with the following additive package: to 99.5 parts of the polyethylene composition, 0.1 part of Irgafos™ 168, 0.25 part of Irganox™ 1330, 0.05 part of zinc oxide and 0.1 part of Evernox™ MD1024 were added.
-
Table 2 MI2 (g/10 min) 1.17 MI5 (g/10 min) 3.1 density (kg/m3) 937.2 molecular weight distribution (Mw/Mn) 4.0 tensile Modulus (MPa) 668 CDBI (%) 65.8 dynamic viscosity at 100 rad/s, η*(100) (Pa.s) 1705 dynamic viscosity at 0.1 rad/s, n*(0.1) (Pa.s) 6734 ratio η*(0.1)/η*(100) 3.95 G' (G"= 500 Pa) (Pa) 56.9 - Density (D) of the polyethylene was measured according to ISO 1183-1 (Method A) and the sample plaque was prepared according to ASTM D4703 (Condition C) where it was cooled under pressure at a cooling rate of 15°C/min from 190°C to 40°C.
- Melt Index MI2 and MI5 were measured using the procedures of ISO 1 133 at 190°C using loads of 2.16 and 5 kg, respectively.
- Tensile Modulus was measured at 23°C and a deformation rate of 1 mm/min on ISO 1B specimens according to ISO 527-2 standard.
- Rheological measurements were carried out on an oscillatory rheometer (e.g., Rheometrics RDS-2, ARES) with 25mm diameter parallel plates in a dynamic mode under an inert (nitrogen) atmosphere. For all experiments, the rheometer was thermally stable at 190°C for at least 30 minutes before inserting the appropriately stabilised (with antioxidant additives), compression-moulded sample of resin onto the parallel plates. The plates were then closed with a positive normal force registered on the meter to ensure good contact. After about 5 minutes at 190°C, the plates were lightly compressed and the surplus polymer at the circumference of the plates trimmed. A further 10 minutes was allowed for thermal stability and for the normal force to decrease back to zero.
- Two strain sweep (SS) experiments were initially carried out at 190°C under nitrogen to determine the linear viscoelastic strain that would generate a torque signal which is greater than 10% of the lower scale of the transducer, over the full frequency (e.g. 0.01 to 100 rad/s) range. The first SS experiment was carried out with a low applied frequency of 0.1 rad/s so as to determine the sensitivity of the torque at low frequency. The second SS experiment was carried out with a high applied frequency of 100 rad/s to ensure that the selected applied strain is well within the linear viscoelastic region of the polymer so that the oscillatory rheological measurements do not induce structural changes to the polymer during testing. In addition, a time sweep (TS) experiment was carried out with a low applied frequency of 0.1 rad/s at the selected strain under nitrogen (as determined by the SS experiments) to check the stability of the sample during testing.
- The frequency sweep (FS) experiment was then carried out at 190°C using the above appropriately selected strain level between dynamic frequencies range of 10-2 to 100 rad/s under a nitrogen atmosphere. The complex dynamic shear viscosities, η*(100) in Pa.s, at dynamic frequency of 100 rad/s, and η*(0.1), at a dynamic frequency of 0.1 rad/s, were determined directly from the viscosity data of the frequency sweep (FS) experiment measured at 190°C.
- The frequency sweep (FS) experiment is then carried out at 190°C using the above appropriately selected strain level and the dynamic rheological data thus measured are then analysed using the rheometer software (viz., Rheometrics RHIOS V4.4 or Orchestrator Software) to determine the melt elastic modulus G'(G" = 500 Pa) at a constant, reference value (500 Pa) of melt viscous modulus (G").
- Apparent molecular weight distribution and associated averages, uncorrected for long chain branching, were determined by Gel Permeation (or Size Exclusion) Chromatography according to ISO 16014-1 , ISO 16014-2 and 16014-4, using a PL 220 of Polymer Laboratories with 4 columns WATERS STYRAGEL HMW 6E of 30 cm length and 1 guard column Waters Styragel 4.6 x 30 mm and a differential refractometer detector. The solvent used was 1,2,4 Trichlorobenzene at 150°C, stabilised with BHT, of 0.2 g/litre concentration.
- Polymer solutions of 0.8 g/litre concentration were prepared at 160°C for one hour with stirring only at the last 30 minutes. The nominal injection volume was set at 400µl and the nominal flow rate was 1 ml/min.
- A relative calibration was constructed using 13 narrow molecular weight linear polystyrene standards:
PS Standard Molecular Weight 1 7 520 000 2 4 290 000 3 2 630 000 4 1 270 000 5 706 000 6 355 000 7 190 000 8 114 000 9 43 700 10 18 600 11 10 900 12 6 520 13 2 950 - The elution volume, V, was recorded for each PS standards. The PS molecular weight was then converted to PE equivalent using the following Mark Houwink parameters :
. kPS =1.21 10-4 dl g-1 αPS= 0.707, kPE= 3.92.10-4 dl g-1, αPE= 0.725. - The calibration curve Mw Pp = f(V) was then fitted with a first order linear equation. All the calculations are done with Empower 2 software from Waters.
- Temperature Rising Elution Fractionation (TREF), as described for example in Wild et al., J. Poly. Sci., Poly. Phys. Ed., vol. 20, p. 441 (1982), is a technique used for the analysis of the comonomer (composition) distribution in semi-crystalline polymers and more specifically for the analysis of the short chain branching distribution (SCBD) in linear low density polyethylene (LLDPE) and tacticity in polypropylene (PP).
- In particular, the TREF solubility distribution curve for a copolymer can be readily used to determine a "Composition Distribution Breadth Index" ("CDBI") which has been defined (e.g., in
US Patent No. 5206075 andPCT publication WO93/03090 - The TREF apparatus was supplied by the PolymerChar Company with the following components:
- ∘ A special oven to perform the crystallization and elution temperature ramps. An Agilent GC 7890 oven which is split in two parts: the top oven (where the Valco valves, a vapor sensor are installed) and the main oven where the five 60 mL vessels as well as the TREF column are installed. The polymer samples are dissolved in these vessels.
- ∘ The TREF column, size: 7.8 mm (internal diameter) x 15 cm (length), packed with stainless steal beads (HPLC column).
- ∘ An infrared detector.
- ∘ A dispenser (25 mL syringe).
- ∘ An Agilent Isocratic 1200 series pump.
- ∘ A 2.5 L solvent bottle (TCB).
- ∘ A 2.5 L waste bottle for the contaminated solvent.
- ∘ A computer with the software developed by PolymerChar to program analysis, for acquisition and data processing.
- The copolymer of example 1 was extruded in various standard pipe dimensions, and the properties of the pipes were evaluated according to the relevant standard methods.
- Chlorine resistance was performed on 16 mm SDR7.4 pipes in accordance with ASTM F2023 standard allowing the time to failure to be extrapolated for different oxidation classification codes for examples CL1, CL3 and CL5. Based on the data of Table 3, the regression analysis in accordance with ASTM F2023 and ASTMF2769-10 makes it possible to calculate the regression equation (1) as well as the extrapolated time-to-failure for the different classification codes (Table 4).
Table 3 Temperature (°C) Pressure (bar) Hoop Stress (MPa) Test time (h) Status 115 5.5 2.15 906 failure 115 5.5 2.16 918 failure 115 4.1 1.63 726 failure 115 4.1 1.65 763 failure 115 2.8 1.08 1036 failure 115 2.8 1.07 1072 failure 105 5.5 2.15 2492 failure 105 5.5 2.13 2561 failure 105 4.1 1.61 2582 failure 105 4.1 1.61 2701 failure 95 4.1 1.60 9922 failure 95 4.1 1.59 10423 failure Note: all failures appear to be typical of chlorine induced brittle oxidative failure. From observations, the failures initiated on the inner pipe surface in the form of micro-cracks that propagated through the pipe wall to result in ultimate failure. - Where failure time is in hours, T in degrees Kelvin and hoop stress is in MPa
Table 4: extrapolated time-to-failure values at 5.5 bar for 16x1.8 mm pipe Oxidative resistance classification code Extrapolation conditions Extrapolated time-to-failure (in years) Minimum requirement for F2769 (years) CL5 100% at 60°C (140°F) 140 50 CL3 50% at 60°C (140°F) and 50% at 23°C (73°F) 270 50 CL1 25% at 60°C (140°F) and 75% at 23°C (73°F) 540 50 - 100% at 82°C (180°F) 5.4 - - Pipe Creep resistance was evaluated according to ISO 1167 on 32 mm SDR11 pipes. The pipe pressure resistance was been measured at 110 °C at a hoop stress of 2.6 MPa, and no failure was observed after about 20000 h testing. The results of the pressure testings carried out at 110°C are summarised in Table 5 (illustration for 2.8 MPa < hoop stress < 2.5 MPa, only.
Table 5 : pipe pressure testing at 110°C Test Hoop stress (MPa) Failure time (h) Type 1 2.77 > 6179 Stopped 2 2.76 4648 Ductile 3 2.76 4146 Ductile 4 2.73 > 6179 Stopped 5 2.71 > 7188 Stopped 6 2.71 9900 Ductile 7 2.70 > 6179 Stopped 8 2.68 > 20179 On-going 9 2.66 > 6179 Stopped 10 2.60 > 9035 Stopped 11 2.56 > 9035 Stopped 12 2.52 > 9035 stopped 13 2.50 > 20179 On-going - Resistance to slow crack growth was evaluated according to ISO 13479 standard at 80°C and 9.2 bar on 110 mm SDR11 notched pipes. Brittle type failure was recorded after 5400 h.
- Resistance to rapid crack propagation was evaluated in accordance with EN ISO 13477 standard (RCP-S4 test). Tests were performed on 110 mm SDR11 pipes having a 0.85 m length. The pipes samples were conditioned for at least 6h in a freezer before testing. Compressed air was used as the pressure medium (13 pressure chambers).
The crack length, l c, was measured following the pipe axis from the centre of the striker blade. A crack length, l c, higher than 4.7 times the pipe outer diameter, d n, was defined as a crack propagation. Results of the tests are summarised in Table 6.Table 6: Pipe sample Temperature (°C) Pressure (bar) Result 1 0 6 Crack arrest 2 0 10 Crack arrest 3 -2.5 5 Crack arrest 4 -5 5 Crack propagation 5 -10 5 Crack propagation
The critical temperature Tc of the polyethylene pipes of the invention at a pressure of 5 bars is determined as -2.5°C. - In another embodiment, inventive compositions are also suitable for the manufacture of pipe articles having an MRS classification (Minimum Required Strength at 20°C for 50 years) according to standard ISO 12162 and ISO 9080 evaluation of at least 8.0 MPa.
Equipment | |
Column size (mm) | 7.8 (diameter) x 150 (length) |
Solvent | TCB |
Packing beads | Stainless steel |
Detector | IR |
Wavelength (µm) | 3.42 |
Sample preparation | |
Concentration of the PE solution (mg/ml) | 3.2 |
Injected volume on the column (ml) | 0.4 |
Dissolution temperature (°C) | 150 |
Crystallization step | |
Temperature range (°C) | 95 - 35 |
Crystallization rate (°C/min) | 0.5 |
Annealed time (min) | 20 min at 35°C |
Elution step | |
Elution rate (ml/min) | 0.5 (continuous) |
Temperature range (°C) | 35 - 120 |
Claims (16)
- A pipe having an outer diameter of from 90 to 630 mm and a minimum wall thickness higher than 3.6mm, said pipe having(a) an extrapolated time-to-failure according to ASTM F2023 and ASTM F2769-10 (performed on 16 mm SDR 7.4 pipe) of at least 50 years (for classification code CL5),(b) a time to failure according to ISO 1167 (performed on 32 mm SDR 11 pipe) of at least 10000 hours (110°C under hoop stress of 2.6 MPa), and(c) a resistance to slow crack growth according to ISO 13479 (80°C, 9.2 bar, performed on 110 mm SDR 11 pipe) of at least 5000 hrs,said pipe comprising a copolymer of ethylene and an a-olefin, said copolymer characterized in having a unimodal molecular weight distribution and(a) a density (D) in the range 933 - 948 kg/m3(b) a melt index (MI2) in the range 0.15 - 2.0 g/10 min, and(c) a melt elastic modulus G' (G"= 500 Pa) in the range 40 to 150 Pa.
- A pipe according to claim 1 having an extrapolated time-to-failure according to ASTM F2023 and ASTM F2769-10 of at least 60 years (for classification code CL5),
- A pipe according to either of the preceding claims having a MRS classification according to ISO 9080 of at least 8.0 MPa.
- A pipe according to any of the preceding claims exhibiting a halting of crack propagation at an internal pressure equal to at least 10 bars, as measured at 0°C on a pipe of diameter 110 mm and thickness 10 mm according to method S4 described in ISO 13477:2008.
- A pipe according to any of the preceding claims having an outer diameter from 110 to 315 mm.
- A pipe according to any of the preceding claims having a minimum wall thickness between 6.3 and 28.6 mm, and more preferably between 10 and 20 mm.
- A pipe according to any of the preceding claims wherein the copolymer has a density (D) in the range 933 - 940 kg/cm3and preferably in the range 935 - 940 kg/cm3.
- A pipe according to any of the preceding claims wherein the copolymer has a melt index (MI2) in the range 0.8 - 1.5 g/10 min. and preferably in the range 1.0 - 1.3 g/10 min.
- A pipe according to any of the preceding claims wherein the copolymer has a melt index (MI5) in the range 0.5 to 6.0, preferably in the range 1.0 to 5.0 and most preferably in the range 2.0 to 4.0.
- A pipe according to any of the preceding claims wherein the copolymer has a ratio of complex dynamic shear viscosities η*(0.1)/η*(100) in the range 1.5 to 5.5 preferably in the range 2.0 - 5.0 and most preferably in the range 2.5 - 4.5.
- A pipe according to any of the preceding claims wherein the copolymer is prepared by use of a single site catalyst system.
- A pipe according to any of the preceding claims further comprising an antioxidant system comprising(a) a first antioxidant,(b) a second antioxidant,(c) at least one metal deactivator, and optionally(d) an acid scavenger.
- A pipe according to claim 12 wherein the antioxidant system comprises
(a) 0.01 - 0.3 parts, (b) 0.05 - 1 parts and (c) 0.01 - 0.3 parts and (d) < 0.25 parts per 100 parts of the polymer composition. - A pipe according to claim 12 or 13 comprising 0.1 parts of (a), 0.25 parts of (b) 0.1 part of (c) and 0.05 parts of (d).
- A pipe according to claim 12 wherein (a) is a phosphite, (b) is a hindered phenol and (c) is a hydrazine.
- A pipe according to claim 12 wherein the acid scavenger is zinc oxide.
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GB201213728A GB201213728D0 (en) | 2012-08-02 | 2012-08-02 | Pipes |
PCT/EP2013/066154 WO2014020096A1 (en) | 2012-08-02 | 2013-08-01 | Pipes |
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US20190071561A1 (en) * | 2016-02-02 | 2019-03-07 | Sabic Global Technologies B.V. | Pipe produced with a polymer composition comprising a polyethylen |
US11479624B2 (en) | 2017-11-17 | 2022-10-25 | Exxonmobil Chemical Patents Inc. | PE-RT pipes and processes for making the same |
US10948377B2 (en) * | 2018-10-18 | 2021-03-16 | Aquarius Spectrum Ltd. | Methods circuits assemblies devices systems and functionally associated machine executable code for mechanical failure classification condition assessment and remediation recommendation |
US11898705B2 (en) | 2018-10-18 | 2024-02-13 | Aquarius Spectrum Ltd. | System and method for mechanical failure classification, condition assessment and remediation recommendation |
US11846370B2 (en) | 2019-03-26 | 2023-12-19 | Titeflex Corporation | Multilayer composite pipe and pipe assemblies including reflective insulation |
CN113795368A (en) * | 2019-05-02 | 2021-12-14 | Sabic环球技术有限责任公司 | Pipe for conveying chlorinated water |
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GB1476480A (en) | 1973-07-18 | 1977-06-16 | Du Pont Canada | Ethylene polymers for large diameter pipe |
EP0905146B1 (en) | 1997-09-27 | 2002-10-09 | ATOFINA Research | Production of polyethylene having improved crack and/or impact resistance |
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CA2560435C (en) * | 2004-03-26 | 2011-05-24 | Borealis Technology Oy | A multimodal polyethylene polymer composition and its use in the production of pipes |
US7625982B2 (en) | 2005-08-22 | 2009-12-01 | Chevron Phillips Chemical Company Lp | Multimodal polyethylene compositions and pipe made from same |
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